Treatment of gases



May 8, 1945- A. .1. L. HUTcHxNsoN ET Al. 2,375,560

TREATMENT OF GASES Filed Oct. 27, 1941 3 Sheets-Sheet l 277 c @n I ga 4j4 4%- u-M s 60ern-e715? 713:07/50 /0 $0 V @mme //7 @may C mi ,l .39 W

aaa-P /Zd /2 /3 37 28g. )30 4 5TH/Unze (blew/fr (kP/wry @mfp May 8,1945- lA. J. L. HuTcHlNsoN ETAL 2,375,550

TREATMENT 0F GASES Filed Oct. 27, 1941 3 Sheets-Sheet 3 @gli Maw?SEP/@Enne Patented May 8, 1945 TREATMENT oF GAsEs Arthur J. L. Buschmannma 1ra c. Bechtola, Las

Angeles, Calif., assignors to The Fluor Corporation, Ltd., Los Angeles,Calit, a corporation of California Application October 247, 1941, SerialN0. 416,775

Claims.

' ii; e., water-addition products), or of normally gaseous mixtures ofconstituents, one or more of which form solid hydrates, with reagentswhose effect upon, or reaction with, the substance or mixtureconstituent is improved by their being in a condition of high molecularconcentration. The invention contemplates new methods whereby suchmolecular concentration is obtained as a' result of solid hydrateformation, and the substance or gas mixture constituent is treated witha reagent when thus concentrated.

Various processes are used for treating gas with a reagent to producesome desired effect upon the gas, as to remove impurities therefrom.Illustrative are methods for removing acidic impurities including carbondioxide, hydrogen sulphide, and sulphur dioxide, or inert gases such asnitrogen and helium, from gaseous mixtures such as natural gas,` andcertain of the same impurities from oil refinery gases. Such processesoperate to contact the gas, as such, with the treating reagent, andnecessitate the use of equipment designed particularly to bring the gasinto very intimate and repeated contacts with the reagent. One principalreason for this is that the constituents oi the gas to be treated orremoved by the reagent, are in a state of relatively great moleculardispersion since they are gaseous, and usually such dispersion `is madestill greater by mixture or dilution with other gas. Accordingly, sincethe effectiveness of the reagent is dependent upon its ability to reachor contact the molecules of the substance to be acted upon by thereagent, it becomes necessary to use a treating system wherein thereagent has repeated opportunities to contact the gas, as by the use ofseries of bubble trays, liquid sprays and various other known devices.Even then, however, the treating agent is not afforded an opportunityfor most eillcient action, from standpoints of time or completeness ofaction or reaction, because of the inherent state of moleculardispersion of the substance to be contacted.

In its more general aspects, the present invention Vcontemplateseffecting molecular concentration of a normally gaseous substance, orone or more constituents of a gaseous mixture, for treatment by areagent without limitation as to the specific purpose or composition ofthe reagent, so long as the eillciency of the reagent is enhanced bymolecular concentration of the substance on which the reagent isintended `to act.

Therefore, it is merely by way of illustration that we may refertypically to the treatment of hydrocarbon gases such as natural gas, orgases from straight-run or cracking plants, by a reagent capable ofreacting with and removing acidic impurities of the nature indicatedabove, or any other constituents such as sulphur-containing hydrocarbonswith which the reagent may be reactive. Typical of contemplated reagentsare basic solutions, e. g., water solutions o1' caustic soda or otherreactive metal hydroxides, basic or acidic saltfsolutions, or for somepurposes, solutions of acidic reagents where the gas contains impuritiesof a basic nature. Also contemplated are the various acid gas reactiveamines, particularly the aliphatic amines, of which monoethanolamine,diethanolamine, and triethanolamine are typical.

Briefly, the present processes contemplate forming high molecularconcentrations of the normally gaseous substance to be treated, eitherin solid form, or iiuid phase (liquid or gas), by virtue of theconversion of a portion or all of the hydrate-forming constituents ofthe gas, into solid form. The concentration is in the solid phase whenthe substance to be treated is-itself converted into the hydrate.Otherwise, the conoen- 1 tration may be of a subtractive nature in thesense that residual fluid remaining after hydra,- tion of someconstituents of the gas, Vis concentrated by elimination from the iluidphase of those constituents converted to hydrates. Under circumstancesinvolving such subtractive corrigen;- tration, as the term has beenexplained, the ating eillciency of the reagent is enhanced bygY actionupon or reaction with a constituent moe lecularly concentrated in liquidphase, or in gaseous phase, depending upon the particular conditionsexistinginprocessing a. given gas.j The degree of molecularconcentration is ofcourse least in the gaseous phase, but neverthelessit may be far greater than the corresponding concentration in theuntreated gas, wherein particular constituents may be greatly diluted byother, gaseous substances. v

Particular methods whereby the constituents of the raw gas may betreated by contacting the reagent with separated hydrates, or with agasor gaseous mixture undergoing hydration; be understood to betteradvantage without necessity forfiurther preliminary discussiinufroin`the detailedv description to follow. Reference iswzhad throughout thedescription to the accompanying drawings, in which: Y l

Fig. 1 illustrates a relatively simple system in which the gasconstituents to be treated are concentrated by the formation of hydrateswhich are accumulated in a treating chamber;

Fig. 2 shows a combined treating and distillate recovery systemaccording to which hydrates being continuously separated fromnon-hydrated constituents of the gas, are subjected to continuoustreatment by the reagent;

Fig. 3 illustrates a process whereby the constituents of a partially ortotally hydrated gas stream are treated with reagent prior to separationof the hydrates from the stream;

Fig. 4 illustrates a similar system involving continuous decompositionof the hydrates and separation of the liberated gas;

Fig. 5 illustrates a further variational form of the invention in whichthe treating reagent is introduced with water to the raw gas stream; and

Fig. 6 illustrates a similar system wherein the hydrates arecontinuously decomposed and the liberated gas separated from theresidue.

The system shown in Fig. 1 involves a relatively simple method forconverting constituents oi' the gas to be treated, into their solidhydrates, and for isolating or separating the hydrates so that thetreating reagent acts upon constituents of the original gas thathavebeen concentrated, either in solid or fluid phase, by virtue of thehydration. This type of system also may be employed to serve thepurposes of the invention disclosed in the copending HutchinsonVapplication, Serial No. 407,036, filed August 15, 1941.

'Ihe raw gas containing constitutents to be treated, may be introducedthrough line I0 to the converter II Without precooling, where the normalgas temperature is sufficiently low to permit proper conversiontemperatures in the converter. Otherwise the gas may be precooled bypassage through the cooler I2a. The gas stream introduced to theconverter is intimately admixed with finely divided Water particlesinjected from line I2 in the form of a spray or mist at the outlets I3.The water desirably may be intimately admixed or emulsied with anon-aqueous carrier liquid, such as kerosene distillate or gas oil, or alight mineral oil fraction, as an aid in promoting ne particledispersion of the water and to facilitate transfer of the hydrateparticles from the converter to the treating chamber by entrainmentofthe particles in the carrier liquid. Generally speaking, temperatureand pressure conditions in 'the converter may be controlled inaccordance with the desired conversion into hydrates of thehydrate-forming constituents of the gas. For purposes of illustration,we may assume that gas introduced through line III is a natural gas,although the invention ,is not so limited, consisting of hydrocarbonsincluded in the methane, ethane, propane, and butane series (includingisomers), together with impurities such as carbon dioxide, hydrogensulphide, and sulphur dioxide, or in fact any constituents or impuritieswhich are to be removed by treatment with a reagent as later described.Merely as illustrative, the temperature of the water-gas mixture in theconverter may range between about F. to 40 F. and the pressure between25 to 650 lbs. per sq. in. gauge, depending upon the composition of thegas. The converter chamber I I may be thermally insulated or cooled in,any suitable manner, as by the provision of a jacket diagrammaticallyindicated at The hydrate particles formed in the converter II areentrained in the stream of carrier liquid and discharged from the bottomof the converter through line I8 into pipe I6, through which the.mixture is .transferred to the treating chamber` Il. Removal of thehydrate-carrier liquid mix-wgpermeable oor 20 through which the carrierliquid is withdrawn to the bottom outlet line 21. 'I'he carrier liquidthen maybe recirculated by pump 22 through cooler 23, wherein the liquidmay be cooled to a temperature above or below the freezing temperatureof water. The cooled carrier liquid thence recirculates through line 24for delivery to line I9, and to be admixed in line I2 with waterintroduced to the system through line 25. A portion of the cooledcarrier liquid may be circulated through lines 26 and 21 into Jacket 28or coil 29 for purposes of cooling or refrigerating the treatingvchamber to stabilize the accumulated hydrates. The carrier liquid thenrecirculates through lines 30 or 3l into pipe 32 returning to line 2l.An independent cooling (or heating) fluid may be passed through thetreating chamber cooling system from inlet 33 to the outlet 34.

'I'he concentration of those constituents of the raw gas to be treatedwith a selected reagent, mayy occur in the form of the hydrates. ofthose constituents accumulated in the treating chamber I1.

The treating process may serve not only the purpose of contacting thehydrated constituents with the reagent, but also to decompose a portionor all of the hydrates toliberate gas. Thus, for example, after thehydrates have been accumulated in chamber I1, valves 35 and 38 may beclosed, and the reagent, or a solution of the reagent proper, introducedto the chamber through lines 31 and I8 so asto directly contact and actupon or reactl with the hydrated constituents to be treated. The reagentmay be heated, as by passage through the heater 38, to a temperaturesufflcient to cause the desired decomposition of the hydrates. Insteadof using heated reagents, unheated reagent may be introduced through theheater by-pass line 39 and any desired heating of the hydratesaccomplished by circulation of heating uid through coil 28. Followingtreatment of the hydrates and liberation of the clean gas through thevalved outlet line 40, the residual water and spent reagent may bewithdrawn from the chamber through the bottom outlet 2| and valved line4 I Concentration of constituents of the raw gas to be treated may alsooccur in a subtractive sense, i. e., by a process of concentrationresulting from the conversion of other constituents of the gas to their.solid hydrates. To illustrate, the conditions existing in the converterI I may transform into hydrates those constituents of the gas which arenot to be reagent-treated, or which it may be desired to treatseparately from residual unconverted constituents o! the gas. Thelatter, concentrated by the hydrate formation, may be withdrawn from theconverter through line 42 and suitably treated with the reagent, as bypassing the gas through a chamber 43 to lwhich the reagent is introducedthrough line 44. 'I'he clean treated gas is withdrawn through line 43aand the spent reagent taken from the bottom of the chamber through line43o forA regeneration or other disposal.

The flow diagram of Fig. 2 illustrates a system I similar in certainbroad aspects to that described with reference to Fig. 1, but differingin the method of separating the hydrates from the carrier liquid andnon-hydrated constituents of the gas. and providing for continuousdecomposition of the separated hydrates.

This system further is particularly adapted to the treatment andseparation from the hydrates of non-hydrate forming constituents of theraw aas. such as gasoline fractions, which the raw gas in this instancemay be assumed to contain. 'I'hus the converter lla here servestotransform into hydrates all or -a predetermined portion of the potentialhydrate-forming constituents of the gas, leaving unconvertible andcondensed liquid hydro-carbon fractions of the gas for removal,

i as such, with the carrier liquid and formed hydrates, through lineIlia.

Instead of delivering the hydrates for accumulaton within a separatingzone, as in the previous instance, Fig. 2 shows the carrieryliquid-hydratehydrocarbon stream taken from the converter I la to bedischarged through line lia to a filtering zone, generally indicated at48, within which a continuous stream of the hydrates is removed from anon-hydrated liquid, and transferred through line 41 to a hydratedecomposition chamber or gas generator 48. Here the separating medium isshown typically to comprise a diagrammatically illustrated rotary filterof the usual known type, and comprising a filter drum 49 rotated in thedirection of the arrow and contaned within a housing 58 of sufiiclentstrength to withstand hydrate stabilizing pressures. The stream in line45 is discharged at 5I onto the tlter surface of the drum 49; and by themaintenance. as

usual, of somewhat lower pressure inside the drum. all fluidconstituents of the mixture are `drawn through the filter into the drumand discharged through line 52 to the stripper 53.

In order that the hydrates may be freed of any residual high boilinghydrocarbons that otherwise might contaminate or undeslrably affect thedesired properties of the eas to be generatcd. thl` hydrates separatedon the surface of the filter 49 preferably are washed with a hydrocarbonsolvent before removal from the drum. This washing liquid mayconveniently consist of cooled carrier liquid directed from line 54against the hvdrate crust on the ,lter at a suitable location in advanceof the point at which the hydrate-s are removed, As will be understood.the washingr liquid also is drawn into the filter and discharged throughline 52 to the stripper. The hydrates are `removed from the filter bythe usual scraper edge 55 and immediately are entrained in a stream ofcarrier liquid introduced to the filter through lne F8 to form a mixturethat can be forced by pump 51 through line 41 to chamber 48.

The hydrate-carrier liduid mixture in chamber 48 may be temperaturecontrolled. independently of the treating reagent. bv env suitable meanssuch as heating or coolingr coil 58. and the hydrates may be decomposedand the gas 1`berated at any desired pressure-determined by thetemperature of decomposition and the setting of the back pressure valve59 in the gas outlet line M. According to the system of Fig. 2. thehydrate stream introduced to chamber 48 from line 41 is continuouslycontacted by a stream of the reagent discharged into the chamber throughline 82. As before, the reagent may be preheated to supply Vthroughlines 88 and 84 into separator |88, from the bottom of which the waterand spent reagent are withdrawn through line 88 to suitable equipment,diagrammatically indicated at 81, for regenerating the reagent andseparating it from the water. The reagent thence may be recirculatedthrough line 88 to the treating chamber, and the separated `waterrecycled through line 89 and cooler 18 to the emulsiiler 1 i. Fromseparator 65, the upper stratum carrier voil is recirculated throughline 12, cooler 13 into accumulator 12a. and thence through line 58 toreentrain the hydrates being removed from the filter drum 49.

It is contemplated that where operating conditions permit, vthe carrierliquid, residual water, and spent reagent may be taken from the treatingchamber 48 through line 14 for further treatment in the stripper andfractionatlng system, generallv indicated at 15. According to thismethod of operation, the Huid mixture in line 14 is introduced to thestripper along with the carrier liquid and any liquid non-hydratedfractions` of the original gas, withdrawn from the iilter through line52. By suitably heating the mixture in the stripper, as by coil 18, allmaterials having boiling temperatures lower than that of the carrierliquid, are vaporized and removed through line 11, leaving the separatedcarrier liquid to be recirculated through line 18 to storage zone 19.thence to be taken through the cooler 88 to emulsiiler 1l for return tothe converter lla, and through line 8| for more direct recirculation tothe filtering zone, as will appear.

Where certain types of reagents are used. such as the amines reactivewith acidic constituents of the gas or hydrates, regeneration of thereagent may result from its vaporization from the stripper 53.Typically, the vapor mixture may be passed through condenser 82 and thecondensate, including the reagent, water, and iight hydrocarbons.received within an accumulator 83from which the regenerated reagent andwater are withdrawn through line 84 for further separation orrecirculation to the treating chamber 48. as may he desired. The higherstratum hydrocarbons may be taken off through line 85 to thefractionator 88 and therein subjected to fractional separation into arelatively heavy cut (e. g, stabil'zed gasoline) withdrawn through line81 to final cooler 88. and a light overhead fraction recovered fromcondenser 89 in a receiver 90. 'Ihe light product will be withdrawnthrough line 9| and a portion recirculated to the fractionator throughlnel 92 as reflux, as may be recirculated to stripper 5-'4 through line93 a portion of the condensa-te fed to the fractionator through line 85.As will be understood. suitable means mav he employed for supplying tothe hydrocarbons introduced to the fractionator. heat required tova'oorize the lighter constituents. A base heating coil 94 is shown astypical.

The recirculated carried liquid `and water. to- Eetber with anynecessary make-un water, may be admixed or emulsied in vessel 1| andthence discharged through line 95 into the converter Ila to be admixedwith the gas fed in through line 9i. Any non-hydrated gas released fromthe converter through line 81 may or may not be treated with a reagent,as previously explained with reference to Fig. l. A portion of thecarrier liquid taken from storage 19 through line 8| may be passedthrough chiller 98 into line 89 from which the chilled carrier liquid ismixed with the carrier liquid-hydrate stream being discharged from theconverter through line |5a. A portion of the chilled carrier may bereturned through line 54 to the filter wherein the carrier is dischargedonto the hydrate cake on the drum 49 for the purpose of removing fromthe hydrates, residual high boiling hydrocarbons as previouslyexplained. Where recirculation of carrier liquid to the filtering zonethrough line 12 is not employed, the necessary carrier liquid may besupplied from line 54 through its valved connection with the accumulator12a.

It is also contemplated with respect to the process of Fig. 2 that theseparated hydrates may be treated with the reagent `prior to theirintroduction to the treating chamber 48. In some instances it may bedesirable to contact the hydrate iilter cake with a treating reagent ofsuitable character, as by discharging the reagent from line. |60 at asuitable point on the iilter surface in advance of the location I atwhich the liquid-hydrate mixture is directed against the filter. It willbe understood that the hydrate cake maybe treated with the` washingliquid or hydrocarbon solvent, before or after contacting the hydrateswith the reagent. Merely as illustrative, the reagent discharge fromline |60 is shown to occur beyond the point of discharge from line 45and in advance of the location at which the washing liquid from line 54contacts the hydrate cake. The outlets from the several lines may ofcourse be spaced about the filter surface as desired.

Figs. 3 and 4 illustrate another type of` treating system embodying theinvention, whereby the reagent is introduced to a mixture of hydratedand non-hydrated constituents of the gas prior to their separation. Asbefore, concentration of the constituents desired to be treated mayvresult from the hydration of those constituents, or from concentrationAin fluid lhase by subtractive hydration of other constituents of thegas. Here the gas and water, or watercarrier liquid mixture, are fedthrough lines |03 and |04 into a mixing conduit |05 from which thegas-water mixture passes into a suitable cooling zone, shown typicallyas vessel |06 containing a cooling coil |01 through which a coolingfluid is circulated to and from the conventionally illustratedrefrigerationsystem |80. By proper control of the pressure andtemperature conditions, all or part of the hydrate-forming constituentsoi' the gas are converted into solid Vhydrates, which in Fig. 3 aretransferred in the able source, such as container ||2 to which thevreagent is introduced from line H3. If the reagent-requires a solvent,such as water, the latter may be fed to the container as at ||4. With orwithout precooling, as by coil IIB in the container, ther-'reagent maybe discharged at a` during the time the materials are in contact' withinthe separating zone. All gases present in the mixture may be suitablyremoved before introduction of the stream to the separator, as byplacing in line |08 beyond 'the mixer H3 a gas separator |20 from whichthe gas flows through line |2|, and from which the liquid is dischargedthrough the usual liquid level controlled valve |22 in line |08. All orpart of the gas thence may be recycled through line |23 to the raw gasline |03, or the separated gas may be discharged from the system throughthe outlet line |24. During this time, valve |25 in the gas outlet ofthe separator being charged with hydrates, is kept closed.

The on-stream separator may be filled with hydrates by permitting thelatter to settle upon and accumulate above a duid-permeable floor |26,and drawing off the carrier liquid through lines |21 and |28 forrecirculation to the water and carrier liquid storage |29. The higherspeciiic gravity spent treating reagent or solution may be withdrawnfrom the bottom of the separator through line |30 for disposal as wastesolution or to be regenerated. After the separator is iilled withhydrates, its valves I 3| and |82 are closed and the mixing passagestream directed through line |08 into the other separator, from which aprevious charge of hydrates may have been removed. 'I'he accumulatedhydrates may be decomposed, as by heat supplied through coil |32, toliberate the clean gas to the outlet line |24, or the hydrates may betreated or disposed of in any other desired manner and lfor particularpurposes with which the present invention is not concerned.

In the system shown in Fig. 4, the gas, Water, and carrier liquid areadmixed to produce a hydrate-,forming composition, the mixture cooledand treated with a reagent introduced to the responding stage in thesystem of Fig. 3. Fig.

4 differs primarily in the provision for continuousv decomposition ofthe hydrates and separation of the liberated gas' from the carrierliquid and spent treatingv solution. Here the stream beyond the mixer||8 is discharged through line |08a into a separating zone |33 which mayconsistl of a stripper column operating at relatively low,

pressure beyond the valve |34 at which the hydrates will decompose andliberate the hydrated gas to the outlet line |35. Any desired backpressure may be maintained on the stripper by valve |38 in the outletline. Suitable provision may be is taken off through line |4| andreeirculated through cooler |42 and line |43 to be again mixed 2,875,500Y with water in container |53 and injected through ter and gas mixture,specifically and preferably by adding the reagent to the water, or the'water and carrier liquid, and injecting the resulting mixture into theraw gas stream. Thus, as shown in Fig. 5, the water and reagent enterthe mixing tank |45 through lines |46 and |41, and then pass through thevalved line |40 and the mixer |49 to be admixed or emulsiiied with thecarrier liquid being recirculated through lineV |28. When introducedthrough line |04 to the gas stream in line |05, the reagent is caused toact upon constituents of the gas to be treated, throughout the hydrateformation stage.

Similarly in Fig. 6, water and reagent delivered through lines |50 and|5| to the container |52 are admixed or emulsiiied with carrier liquiddelivered through line |43, and the resulting mixture taken through line|04 into the raw gas stream.

The expression undesired component as used in the claims is intended, ina broad sense, to mean a component which it Vis not desired, forany'reason, to retain, or to retain as such, in the mixture treated, andis intended in a narrower sense to mean a component which may beobjectionableper se, as because of its own particular composition,properties, or lack of qualities desired in the treated gas.

We claim:

1. The method of treating a normally gaseous mixture containinghydrate-forming components including an undesired component, thatincludes converting said components to their solid hydrates, treatingthe resulting hydrate mixture with va reagent reactive with'saidundesired coml ponent, separating the reaction product, and recoveringthe puried remaining material.

2. The method of treating a normally gaseous mixture containinghydrate-forming hydrocarbon components and an undesired hydrate-forming,non-hydrocarbon impurity to beremoved from the mixture, that includesconverting said components and impurity to their solid hydrates treatingthe resulting hydrate mixture with a reagent reactive with saidimpurity, separating the reaction product, and recovering the purifiedremaining material,

3. The method of treating a normally gaseous mixture containinghydrate-forming hydrocarbon components and an undesired hydrate-forming,acidic impurity to be removed from the mixture, that includes convertingsaid components and impurity to their solid hydrates, treating theresulting hydrate mixture with an alkaline reagent reactive with saidimpurity, separating the reaction product, and recovering the puriedremaining material.

4. The method of treating a normally gaseous mixture containinghydrate-forming hydrocarbon components and an undesired hydrateforming,acidic impurity to Vbe removed from the mixture, that includesconverting said components and impurity to their solid hydrates,treating the resulting hydrate mixture with an amine reagent reactivewith said impurity, separating the reaction product, and recovering thepuried remainining material.

f5. The method of treating a normally gaseous mixture containinghydrate-forming components including a hydrocarbon and an undesiredcomponent of the group consisting oi' hydrogen sulphide, carbon dioxide,and sulphur dioxide, that includes converting said components into theirsolid hydrates, treating the resulting hydrate mixture with a reagentreactive with said unldesired component, separating the reactionproduct, and recovering the purified remaining material.

6. The method of treating a normally gaseous mixture containinghydrate-forming components including an undesired component, thatincludes converting said components to their solid hydrates, treatingthe resulting hydrate mixture with a reagent reactive with saidundesired component, separating the spent reagent from the purifiedremaining material, recovering said puried remaining material,regenerating the reagent, and returning the regenerated reagent fortreatment of additional hydrated components of the first mentionedmixture.

7. The method of treating a normally gaseous mixture containinghydrate-forming components including an undesired component, thatincludes converting said components to their solid hydrates and therebyforming a mixture of the hydrates with non-hydrated fluid `components ofthe iirst mentioned mixture, treating the resulting hydrate-fluidmixture with a reagent reactive with said undesired component,separating the reaction product, and recovering the purirled remainingmaterial.

8. The method of treating a normally gaseous mixture containinghydrate-forming components including an undesired component, thatincludes converting said components to their solid hy- 4 drates,separating the hydrates from non-hydrated constituents of the mixture,treating the resulting hydrate mixture with a reagent reactive with saidundesired component, separating the reaction product, and recovering thepurified remaining material.

9. The method of treating a normally gaseous 1 mixture containinghydrate-forming components including an undesired component, thatincludes contacting said mixture with water under temperature andpressure conditions causing formation ofthe hydrates of said component,continuously separating non-hydrated fluid from a stream of thehydrates, treating the resulting hydrate mixture with a reagent reactivewith the hydrated undesired component, separating the reaction product,and recovering the purified remaining material.

10. The method of treating a normally gaseous hydrocarbon mixturecontaining hydrate-forming components including an undesired acidiccomponent, that includes contacting said mixture with Water undertemperature and pressure conditions causing formation of the hydrates ofsaid components, continuously separating gaseous constituents of themixture from the `hydrates, treating the resulting hydrate mixture withareagent reactive with the hydrated undesired component, separating thereaction product` and recovering the purified remaining material.

ll. The method of treating a normally gaseous hydrocarbon mixturecontaining hydrate-forming components including an undesired component,that includes contacting said mixture With water under temperature andpressure conditions causing formation of the hydrates of saidcomponents, separating non-hydrated iiuid from the hydrates and' storingthe hydrates under stabilizing temperature and pressure, treating thestored hydrates with a reagent reactive with the hydrated undesiredcomponent, separating the reaction product, and `recovering the purifledremaining material.

12. The method of treating a normally gaseous mixture containinghydrated-forming components including an undesired component, thatincludes contacting said mixture with Water under temperature andpressure conditions causing formation of the hydrates of saidcomponents, separating non-hydrated fluid from the hydrates, treatingand decomposing all the hydrates with a reagent reactive with thehydrate of said un` desired component, separating the reaction product,and recovering the purified remaining ma-I terial.

13. The method of treating a normally gaseous -mixture containinghydrate-forming components including an undesired component, thatincludes contacting said mixture with water and a waterimmisciblehydrate carrier liquid under temperature and pressure conditions causingformation of said hydrates, separating said carrier liquid from thehydrates, treating the hydrates with a reagent reactive with thehydrated undesired component to remove said undesired component,separating the reaction product, and recovering the purified remainingmaterial.

14. In processing a normally gaseous mixture containing hydrate-formingcomponents including an undesired component, the method that includestreating a stream of said mixture with y water and a reagent undertemperature and pressure conditions causing formation of the hyter, aWater-immiscible carrier liquid, and a reagent`un'der temperature andpressure conditions causing formation of the hydrates of saidcomponents, saidv reagent being reactive with the hydrate of saidundesired component to permit its removaL'separating the reactionproduct, and recoverying thepuried remaining material.

16. In processing a normally gaseous mixture containing hydrate-formingcomponents including an undesired component, the method that includestreating a stream of said mixture with Water, a mineral oil fraction,and a reagent under i containing hydrate-forming components includinganundesired component, the method that includes treating a stream ofsaid mixture with water, a water-immiscible hydrate carrier liquid and areagent to form a mixture of the hydrates of said components andimpurity, passing the resultingrmixture in a state of turbulent flowthrough an elongated passage of relatively small crosssectional area,said reagent being reactive with the hydrate of said impurity to permitits re- A.

moval from the materials mixed therewith, separating the reactionproduct, and recoveringthe purified remaining material.

18. In processing a hydrocarbon gas containing hydrate-formingcomponents and a hydrateforming acidic impurity to be removed, themethod that includes treating a stream of the gas with a mixture ofwater and a reagent to form a mixture of the hydrates of said componentsand impurity, said reagent being reactive with the hydrate of saidimpurity, separating the spentv reagent from the hydrate mixture,recovering lthe purified-remaining material, andrregenerating thereagent and returning it to said stream.

19. In processing a gas containing hydrateforming hydrocarbon componentsand a hydratevincludes treating a stream of said mixture with water, awater immiscible hydrate carrier liquid and a reagent to form a mixtureof the hydrates of said components and impurity, said reagent beingreactive with the hydrate of said impurity, separating the spent reagentand carrier liquid from the hydrate mixture, recovering the purifiedremaining material, separating the spent reagent vand carrier liquid,regenerating the reagent, and returning the regenerated reagent andseparated carrier liquidto said stream.

' IRA C. BECHTOLD. ARTHUR. J. L. HUTCHINSON.

